CN114539699A - Expanded microsphere and polyether polyol toughened 3D printing photocuring resin and preparation method thereof - Google Patents
Expanded microsphere and polyether polyol toughened 3D printing photocuring resin and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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Abstract
The invention discloses an expanded microsphere and polyether polyol toughened 3D printing photocuring resin and a preparation method thereof, wherein the raw materials comprise 50-90% by mass of prepolymer, 7-40% by mass of active diluent, 1-10% by mass of photoinitiator, 1-10% by mass of expanded microsphere and 0.1-2% by mass of polyether polyol. The light-cured resin has high toughness and high strength, and the mechanical strength of parts is improved.
Description
Technical Field
The invention belongs to the field of light-cured resin materials, and relates to a 3D printing light-cured resin toughened by expanded microspheres and polyether polyol and a preparation method thereof.
Background
3D printing technology, also known as additive manufacturing technology, has become a widely used new technology with unparalleled potential since the 20 th century and the 80 th era. The 3D printing basic principle is that a 3D model outputs an STL format file through computer slicing, then the file is guided into a printed piece, a corresponding shape is projected according to a slicing information light source, a graph receiving illumination is converted from liquid into solid, and then materials are added layer by layer to obtain a product. The 3D printing photocuring rapid prototyping technology has the advantages of high curing speed, environmental protection, capability of preparing complex parts and the like, and is therefore valued by more and more people.
However, the photo-cured resin printed matter has defects, and the epoxy resin or acrylic resin used for the photo-cured resin is brittle, so that the product is easy to break and has low strength, and in order to improve the toughness and strength of the photo-cured resin, researchers add nano silicon dioxide, glass fiber, diatomite, graphene oxide and the like into the photo-cured resin, but the inorganic material has poor compatibility with the photo-cured resin, is easy to precipitate, affects the quality of the product, and some fillers improve the toughness and reduce the strength of the material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the expanded microsphere and polyether polyol toughened 3D printing photocureable resin and the preparation method thereof, so that the photocureable resin has high toughness and high strength, and the mechanical strength of parts is improved.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the raw materials comprise, by mass, 50-90% of prepolymer, 7-40% of reactive diluent, 1-10% of photoinitiator, 1-10% of expanded microspheres and 0.1-2% of polyether polyol.
Preferably, the prepolymer is one or a mixture of monofunctional, difunctional and multifunctional prepolymers.
Furthermore, the monofunctional group, bifunctional group and polyfunctional group prepolymer is a composition of two or three of alcohol acrylate, epoxy acrylate, aromatic acrylate, aliphatic acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate and hyperbranched acrylate in any proportion.
Preferably, the reactive diluent is one or more of a combination of monofunctional, difunctional and multifunctional acrylates.
Further, the monofunctional active diluent is one or a plurality of compositions of methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-phenoxyethyl acrylate, methoxy polyethylene glycol monoacrylate, caprolactone acrylate, tetrahydrofuran acrylate and ethoxylated tetrahydrofuran acrylate;
the difunctional reactive diluent is one or a combination of ethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol (400) diacrylate, (3) ethoxylated bisphenol A diacrylate, tripropylene glycol diacrylate and dipropylene glycol diacrylate;
the polyfunctional active diluent is one or a combination of trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate.
Preferably, the photoinitiator is one or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 4-methylbenzophenone, 2-isopropyl thioxanthone, 1-hydroxycyclohexyl phenyl ketone and benzoin dimethyl ether.
Preferably, the expanded microsphere comprises an outer shell and an inner core, wherein the outer shell is a thermoplastic acrylic polymer, and the inner core is an alkane gas.
Furthermore, the diameter of the expanded microsphere is 10-45 microns, and the thickness of the shell is 2-15 microns.
Preferably, the polyether polyol is one or more of POP3630, POP3628, POP3648, POP360, POP210, POP220 and POP 330.
The 3D printing photocuring resin toughened by the expanded microspheres and the polyether polyol comprises the following steps:
step one, adding 1-10% of photoinitiator by mass into 7-40% of reactive diluent to obtain a mixture A;
uniformly stirring a photoinitiator and an active diluent, and then carrying out ultrasonic treatment;
step three, adding 1-10% of expanded microspheres and 0.1-2% of polyether polyol after the photoinitiator is completely dissolved;
step four, continuing ultrasonic treatment until the expanded microspheres and the polyether polyol are uniformly mixed with the mixture A to obtain a mixture B;
and step five, stirring the mixture B for 1-2 hours at the stirring speed of 500-1500 rpm, and then standing until air bubbles in the resin are completely eliminated to obtain the 3D printing photocuring resin.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the expanded microspheres as the filler, and the shell of the expanded microspheres is thermoplastic acrylic resin, and the prepolymer and the reactive diluent in the photocuring system are also acrylic resin, so that the two have good compatibility, and when the content is 1%, the shell is hard acrylic acid which is similar to a reinforcing material, thereby improving the strength of the composite material. Meanwhile, the expanded microspheres with the inner cores of gaseous hydrocarbons are added into the photocuring resin, and after the resin is impacted or bent, the expanded microspheres modify the photocuring resin to change crack propagation paths and form more microcracks to increase the toughness. The polyether polyol can be separated out to form micron-sized particles in the process of curing the epoxy acrylate, so that the toughness of the epoxy acrylate is improved.
Drawings
FIG. 1 is a schematic view of a hole punched in a photo-curable resin without toughening;
FIG. 2 is a schematic view of the drilling of the toughened photocurable resin according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "front," "back," "left," "right," "upper" and "lower" used in the following description refer to directions in the drawings, and the terms "inner" and "outer" refer to directions toward and away from, respectively, the geometric center of a particular component.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The expanded microsphere and polyether polyol toughened 3D printing photocuring resin provided by the invention comprises, by mass, 50-90% of prepolymer, 7-40% of active diluent, 1-10% of photoinitiator, 1-10% of expanded microsphere and 0.1-2% of polyether polyol.
The prepolymer is one or a mixture of monofunctional group, bifunctional group and polyfunctional group.
The monofunctional group, bifunctional group and polyfunctional group prepolymer is a composition of two or three of alcohol acrylate, epoxy acrylate, aromatic acrylate, aliphatic acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate and hyperbranched acrylate in any proportion.
The reactive diluent is one or a combination of monofunctional, difunctional and multifunctional acrylate.
The monofunctional reactive diluent is one or more of methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-phenoxyethyl acrylate, methoxy polyethylene glycol monoacrylate, caprolactone acrylate, tetrahydrofuran acrylate and ethoxylated tetrahydrofuran acrylate.
The difunctional reactive diluent is one or a combination of ethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol (400) diacrylate, (3) ethoxylated bisphenol A diacrylate, tripropylene glycol diacrylate and dipropylene glycol diacrylate.
The polyfunctional active diluent is one or a combination of trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate.
The photoinitiator is one or a mixture of two or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 4-methylbenzophenone, 2-isopropyl thioxanthone, 1-hydroxycyclohexyl phenyl ketone and benzoin dimethyl ether.
Polyether polyols are obtained by polyaddition of an initiator such as an active hydrogen group-containing compound with ethylene oxide, propylene oxide, butylene oxide, etc. under the catalysis of a catalyst.
The polyether polyol is terminated by hydroxyl and has low viscosity, and is one or a mixture of two or more of POP3630, POP3628, POP3648, POP360, POP210, POP220 and POP 330.
The expanded microsphere is a milky physical expanded microsphere and is a special core-shell structure, the shell is a thermoplastic acrylic polymer, the core is generally a gaseous hydrocarbon, the diameter of the expanded microsphere is generally 10-45 micrometers, the thickness of the shell is 2-15 micrometers, and the shell has good resilience and can bear large pressure after the expanded microsphere is heated and expanded, so that the expanded microsphere cannot break and can keep good performance. The outer shell of the expanded microsphere can be softened after being heated, and the hydrocarbon in the shell can be quickly expanded to 20-50 times of the original volume.
The preparation method of the expanded microsphere and polyether polyol toughened 3D printing photocuring resin comprises the following steps:
step one, adding 1-10% of photoinitiator by mass into 7-40% of reactive diluent to obtain a mixture A.
And step two, manually stirring the photoinitiator and the reactive diluent uniformly, and then putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 30-60 minutes.
And step three, adding 1-10% of expanded microspheres and 0.1-2% of polyether polyol after the photoinitiator is completely dissolved.
And step four, continuing to perform ultrasonic treatment for 30-60 minutes until the expanded microspheres and the polyether polyol are uniformly mixed with the mixture A to obtain a mixture B.
And step five, stirring the mixture B for 1-2 hours at the stirring speed of 500-.
Comparative example
The raw material components of the photocurable resin in this example were: 70g of epoxy acrylate, 20g of 1, 6-hexanediol diacrylate and 2g of benzoin dimethyl ether.
The preparation process comprises the following steps: adding 2g of benzoin dimethyl ether into 20g of 1, 6-hexanediol diacrylate, stirring uniformly by hand, then putting into an ultrasonic cleaning machine for ultrasonic treatment for 30 minutes, finally adding epoxy acrylate, stirring for 1 hour in a high-speed stirrer at a stirring speed of 500 rpm, standing until air bubbles in the resin are completely removed, and storing in a dark place for later use.
Example 1
The 3D printing expanded microsphere toughening photocureable resin comprises the following components in parts by weight: 80g of epoxy acrylate, 7g of 1, 6-hexanediol diacrylate, 2g of benzoin dimethyl ether, 10g of expanded microspheres and 1g of polyether polyol.
The preparation process comprises the following steps: adding benzoin dimethyl ether into 1, 6-hexanediol diacrylate, stirring uniformly by hand, then putting into an ultrasonic cleaning machine for ultrasonic treatment for 30 minutes, adding the expanded microspheres and polyether polyol into the mixture after the benzoin dimethyl ether is completely dissolved, continuing to perform ultrasonic treatment for 30 minutes until the expanded microspheres and polyether polyol are uniformly mixed with the mixture, finally adding epoxy acrylate, stirring in a high-speed stirrer for 2 hours at a stirring speed of 750 revolutions per minute, standing until air bubbles in the resin are completely removed, and storing in a dark place for later use.
Example 2
The 3D printing expanded microsphere toughening photocureable resin comprises the following components in parts by weight: 70g of aliphatic acrylic resin, 16.5g of tripropylene glycol diacrylate, 10g of 1-hydroxycyclohexyl phenyl ketone, 3g of expanded microspheres and 0.5g of polyether polyol.
The preparation process comprises the following steps: adding 1-hydroxycyclohexyl phenyl ketone into tripropylene glycol diacrylate, stirring uniformly by hand, then putting into an ultrasonic cleaning machine for ultrasonic treatment for 45 minutes, adding the expanded microspheres and polyether polyol into the mixture after 1-hydroxycyclohexyl phenyl ketone is completely dissolved, continuing to perform ultrasonic treatment for 45 minutes until the expanded microspheres and polyether polyol are uniformly mixed with the mixture, finally adding aliphatic acrylic resin, stirring for 1 hour in a high-speed stirrer at the stirring speed of 1250 revolutions per minute, standing until air bubbles in the resin are completely removed, and storing in a dark place for later use.
Example 3
The 3D printing expanded microsphere toughening photocureable resin comprises the following components in parts by weight: 60g of epoxy acrylate, 31g of ethylene glycol dimethacrylate, 2g of benzoin dimethyl ether, 5g of expanded microspheres and 2g of polyether polyol.
The preparation process comprises the following steps: adding benzoin dimethyl ether into ethylene glycol dimethacrylate, stirring the mixture evenly by hand, putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 60 minutes, adding the expanded microspheres and polyether polyol into the mixture after the benzoin dimethyl ether is completely dissolved, continuing the ultrasonic treatment for 60 minutes until the expanded microspheres and the polyether polyol are mixed evenly with the mixture, finally adding epoxy acrylate, stirring the mixture in a high-speed stirrer for 1.5 hours at the stirring speed of 1000 revolutions per minute, standing the mixture until air bubbles in the resin are completely removed, and storing the mixture in a dark place for later use.
Example 4
The 3D printing expanded microsphere toughening photocureable resin comprises the following components in parts by weight: 50g of aromatic acrylate, 36.5g of pentaerythritol triacrylate, 5g of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 7g of expanded microspheres, 1.5g of polyether polyol.
The preparation process comprises the following steps: adding 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone into pentaerythritol triacrylate, manually stirring uniformly, then placing into an ultrasonic cleaning machine for ultrasonic treatment for 50 minutes, adding the expanded microspheres and polyether polyol into the mixture after the 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone is completely dissolved, continuing ultrasonic treatment for 50 minutes until the expanded microspheres and polyether polyol are uniformly mixed with the mixture, finally adding aromatic acrylic resin, stirring for 2 hours in a high-speed stirrer at the stirring speed of 500 rpm, standing until air bubbles in the resin are completely removed, and storing in a dark place for later use.
Example 5
The 3D printing expanded microsphere toughening photocureable resin comprises the following components in parts by weight: 90g of alcohol acrylate, 7.9g of trimethylolpropane triacrylate, 1g of 2-isopropyl thioxanthone, 1g of expanded microspheres, 0.1g of polyether polyol.
The preparation process comprises the following steps: adding 2-isopropyl thioxanthone into trimethylolpropane triacrylate, stirring uniformly by hand, putting into an ultrasonic cleaning machine for ultrasonic treatment for 35 minutes, adding the expanded microspheres and polyether polyol into the mixture after the 2-isopropyl thioxanthone is completely dissolved, continuing to perform ultrasonic treatment for 35 minutes until the expanded microspheres and polyether polyol are uniformly mixed with the mixture, finally adding aromatic acrylic resin, stirring for 1 hour in a high-speed stirrer at a stirring speed of 1500 rpm, standing until air bubbles in the resin are completely removed, and storing in a dark place for later use.
The photocurable resins obtained from the different components of the above comparative examples and examples were made into dumbbell-shaped tensile members or elongated bending members in a laser rapid prototyping machine according to the national standard, and then the tensile strength and bending strength tests were performed on a universal testing machine, and the data are shown in table 1:
TABLE 1 Performance parameters of the comparative and example products
As can be seen from the above table, with the increasing content of the expanded microspheres, the tensile strength, the flexural strength, the elongation at break and the impact strength of the composite material are increased and then decreased, and the tensile strength and the flexural strength of the photocurable resin containing 1% of the expanded microspheres and 0.1% of polyether polyol in example 1 are the highest, thereby illustrating that the strength is improved by adding 1% of the expanded microspheres, and the strength is enhanced. And when the contents are respectively 1% and 0.1% from the aspects of elongation at break and impact strength under different contents of the expanded microspheres and the polyether polyol, the contents of the expanded microspheres and the polyether polyol are increased, which shows that the expanded microspheres and the polyether polyol can play a toughening role under the condition of respectively adding 1% and 0.1%. Thus, it can be seen that the expanded microspheres at a content of 1% and the polyether polyol at a content of 0.1% both improve the strength and the toughness.
As shown in FIG. 1, the non-toughened resin quickly cracks when punched with a self-tapping screw. As shown in FIG. 2, the toughened resin prepared by the formula and the preparation method of the application is not cracked when a self-tapping screw is used for drilling.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
It is to be understood that the above description is intended to be illustrative, and not restrictive. Many embodiments and many applications other than the examples provided would be apparent to those of skill in the art upon reading the above description. The scope of the present teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are hereby incorporated by reference for all purposes. The omission in the foregoing claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor is it to be construed that applicant does not consider such subject matter to be part of the disclosed inventive subject matter.
Claims (10)
1. The 3D printing photocuring resin toughened by the expanded microspheres and the polyether polyol is characterized in that raw materials comprise 50-90% by mass of prepolymer, 7-40% by mass of active diluent, 1-10% by mass of photoinitiator, 1-10% by mass of expanded microspheres and 0.1-2% by mass of polyether polyol.
2. The expanded microsphere and polyether polyol toughened 3D printing photocurable resin as claimed in claim 1, wherein the prepolymer is one or more of a monofunctional prepolymer, a difunctional prepolymer and a multifunctional prepolymer.
3. The expanded microsphere and polyether polyol toughened 3D printing photocurable resin according to claim 2, wherein the monofunctional, bifunctional and polyfunctional prepolymers are a composition of two or three of alcohol acrylate, epoxy acrylate, aromatic acrylate, aliphatic acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate and hyperbranched acrylate in any proportion.
4. The expanded microsphere and polyether polyol toughened 3D printing photocurable resin according to claim 1, wherein the reactive diluent is one or more of a monofunctional acrylate, a difunctional acrylate and a multifunctional acrylate.
5. The expanded microsphere and polyether polyol toughened 3D printing photocurable resin according to claim 4, wherein the monofunctional reactive diluent is one or more of methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol monoacrylate, caprolactone acrylate, tetrahydrofurfuryl acrylate and ethoxylated tetrahydrofurfuryl acrylate;
the difunctional reactive diluent is one or a combination of ethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol (400) diacrylate, (3) ethoxylated bisphenol A diacrylate, tripropylene glycol diacrylate and dipropylene glycol diacrylate;
the polyfunctional active diluent is one or a combination of trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate.
6. The expanded microsphere and polyether polyol toughened 3D printing photocurable resin according to claim 1, wherein the photoinitiator is one or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 4-methylbenzophenone, 2-isopropyl thioxanthone, 1-hydroxycyclohexyl phenyl ketone and benzoin dimethyl ether.
7. The expanded microsphere and polyether polyol toughened 3D printing photocurable resin according to claim 1, wherein the expanded microsphere comprises an outer shell and an inner core, wherein the outer shell is a thermoplastic acrylic polymer, and the inner core is an alkane gas.
8. The expanded microsphere and polyether polyol toughened 3D printing photocurable resin according to claim 7, wherein the diameter of the expanded microsphere is 10-45 microns and the shell thickness is 2-15 microns.
9. The expanded microsphere and polyether polyol toughened 3D printing light-cured resin according to claim 1, wherein the polyether polyol is one or more of POP3630, POP3628, POP3648, POP360, POP210, POP220 and POP 330.
10. The 3D printing photocuring resin toughened by the expanded microspheres and the polyether polyol is characterized by comprising the following steps of:
step one, adding 1-10% of photoinitiator by mass into 7-40% of reactive diluent to obtain a mixture A;
uniformly stirring a photoinitiator and an active diluent, and then carrying out ultrasonic treatment;
step three, adding 1-10% of expanded microspheres and 0.1-2% of polyether polyol after the photoinitiator is completely dissolved;
step four, continuing ultrasonic treatment until the expanded microspheres and the polyether polyol are uniformly mixed with the mixture A to obtain a mixture B;
and step five, stirring the mixture B for 1-2 hours at the stirring speed of 500-1500 rpm, and then standing until air bubbles in the resin are completely eliminated to obtain the 3D printing photocuring resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024140844A1 (en) * | 2022-12-30 | 2024-07-04 | 中国科学院福建物质结构研究所 | Foamable resin for photocuring 3d printing, preparation method therefor and use thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623265A (en) * | 2016-04-01 | 2016-06-01 | 中国科学院长春应用化学研究所 | Toughener and modified epoxy resin |
| CN110862673A (en) * | 2019-12-03 | 2020-03-06 | 诺思贝瑞新材料科技（苏州）有限公司 | Foaming thermoplastic elastomer material for 3D printing and preparation method thereof |
| CN111253577A (en) * | 2020-01-22 | 2020-06-09 | 黎明化工研究设计院有限责任公司 | Method for preparing modified epoxy acrylate |
| CN111548727A (en) * | 2020-06-12 | 2020-08-18 | 安徽名士达新材料有限公司 | Environment-friendly light-curable wood lacquer and preparation method thereof |
| CN113402969A (en) * | 2021-07-19 | 2021-09-17 | 常州大学 | Thixotropic light-cured circuit board protective resin capable of being automatically peeled off after expansion and application method thereof |
| CN113943408A (en) * | 2020-07-16 | 2022-01-18 | 中国科学院福建物质结构研究所 | Polymer-based composite material foaming part and preparation method thereof |
-
2022
- 2022-03-30 CN CN202210324991.3A patent/CN114539699A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623265A (en) * | 2016-04-01 | 2016-06-01 | 中国科学院长春应用化学研究所 | Toughener and modified epoxy resin |
| CN110862673A (en) * | 2019-12-03 | 2020-03-06 | 诺思贝瑞新材料科技（苏州）有限公司 | Foaming thermoplastic elastomer material for 3D printing and preparation method thereof |
| CN111253577A (en) * | 2020-01-22 | 2020-06-09 | 黎明化工研究设计院有限责任公司 | Method for preparing modified epoxy acrylate |
| CN111548727A (en) * | 2020-06-12 | 2020-08-18 | 安徽名士达新材料有限公司 | Environment-friendly light-curable wood lacquer and preparation method thereof |
| CN113943408A (en) * | 2020-07-16 | 2022-01-18 | 中国科学院福建物质结构研究所 | Polymer-based composite material foaming part and preparation method thereof |
| CN113402969A (en) * | 2021-07-19 | 2021-09-17 | 常州大学 | Thixotropic light-cured circuit board protective resin capable of being automatically peeled off after expansion and application method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024140844A1 (en) * | 2022-12-30 | 2024-07-04 | 中国科学院福建物质结构研究所 | Foamable resin for photocuring 3d printing, preparation method therefor and use thereof |
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